U.S. patent number 9,580,531 [Application Number 14/472,482] was granted by the patent office on 2017-02-28 for poly(ethylene-aliphatic diene) copolymer and preparation method thereof.
This patent grant is currently assigned to KOREA INSTITUTE OF INDUSTRIAL TECHNOLOGY. The grantee listed for this patent is KOREA INSTITUTE OF INDUSTRIAL TECHNOLOGY. Invention is credited to Dong-Gyu Jeon, Dong-Hyun Kim, Jung-Soo Kim, Dong-Jin Yang.
United States Patent |
9,580,531 |
Kim , et al. |
February 28, 2017 |
Poly(ethylene-aliphatic diene) copolymer and preparation method
thereof
Abstract
Disclosed is a poly(ethylene-aliphatic diene) copolymer having
superior miscibility, adhesivity, printability and scratch
resistance, compared to conventional TPO based TPEs or SBC TPEs, by
introducing a variety of functional groups to an end portion of the
ethylene-aliphatic diene copolymer such that the
poly(ethylene-aliphatic diene) copolymer may be utilized in a
variety of fields, and a method thereof.
Inventors: |
Kim; Dong-Hyun (Gunpo-si,
KR), Kim; Jung-Soo (Wonju-si, KR), Yang;
Dong-Jin (Incheon, KR), Jeon; Dong-Gyu (Incheon,
KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
KOREA INSTITUTE OF INDUSTRIAL TECHNOLOGY |
Cheonan-si |
N/A |
KR |
|
|
Assignee: |
KOREA INSTITUTE OF INDUSTRIAL
TECHNOLOGY (Cheonansi, KR)
|
Family
ID: |
52996112 |
Appl.
No.: |
14/472,482 |
Filed: |
August 29, 2014 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20150119532 A1 |
Apr 30, 2015 |
|
Foreign Application Priority Data
|
|
|
|
|
Oct 31, 2013 [KR] |
|
|
10-2013-0130847 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F
236/06 (20130101); C08F 210/02 (20130101); C08F
210/02 (20130101); C08F 236/06 (20130101); C08F
212/08 (20130101); C08F 210/02 (20130101); C08F
236/06 (20130101) |
Current International
Class: |
C08F
236/06 (20060101); C08F 210/02 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Pan et al. Macromolecules 2009, 42, 4391-4393. cited by examiner
.
M. d. F. V. Marques, F. C. Rocha, and N. J. Soto, "Copolymerization
of Ethylene/Diene with Different Metallocene Catalysts",
znaturforsch, Apr. 2006. cited by applicant.
|
Primary Examiner: Kaucher; Mark
Attorney, Agent or Firm: Lex IP Meister, PLLC
Claims
What is claimed is:
1. A poly(ethylene-aliphatic diene) copolymer consisting of
ethylene blocks and aliphatic diene blocks, wherein a portion of
the aliphatic diene block is modified by substituting with a
functional group selected from the group consisting of a sulfide
group, a hydroxyl group, an epoxy group, an amine group, a
carboxylic acid group, a silane group and combinations thereof, the
aliphatic diene block modified by substituting with the functional
group is represented by Formula 1 below: ##STR00009## wherein
R.sub.1 is a linear or branched C1-C20 alkyl group, and R.sub.2 is
selected from OH, C(.dbd.O)OH, S(R.sub.3), NR.sub.4R.sub.5 and
SiR.sub.6R.sub.7R.sub.8, wherein R.sub.1 and R.sub.2 bind together
to form an epoxy ring, R.sub.3 is hydrogen or a C1-C30 alkyl group,
R.sub.4 and R.sub.5 are identical or different, and are hydrogen, a
C1-C10 alkyl group, a C3-C10 cycloalkyl group or an aryl group of
C4-C15, and R.sub.6 to R.sub.8 are identical or different, and are
hydrogen, a C1-C10 alkyl group, a C3-C10 cycloalkyl group or a
C6-C15 aryl group, with the proviso that at least one of R.sub.6 to
R.sub.8 is a C1-C10 alkoxy group or a functional group substituted
with the C1-C10 alkoxy group and all of R.sub.6 to R.sub.8 are not
H.
2. The poly(ethylene-aliphatic diene) copolymer according to claim
1, wherein the aliphatic diene block is polymerized with one
monomer selected from the group consisting of 1,3-butadiene,
isoprene, 2,3-dimethyl-1,3-butadiene, 1,2-dimethyl-1,3-butadiene,
1,4-dimethyl-1,3-butadiene, 1-ethyl-1,3-butadiene,
3-butyl-1,3-octadiene, 1,3-hexadiene, 4-methyl-1,3-pentadiene,
1,3-pentadiene, 3-methyl-1,3-pentadiene,
2,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, and
combinations thereof.
3. The poly(ethylene-aliphatic diene) copolymer according to claim
1, wherein an average molecular weight (Mw) of the
poly(ethylene-aliphatic diene) copolymer is 20,000 to 3,000,000 and
molecular weight distribution of the poly(ethylene-aliphatic diene)
copolymer is 1.2 to 3.0.
4. A method of preparing the poly(ethylene-aliphatic diene)
copolymer according to claim 1 comprising: (a) polymerizing
ethylene with a conjugated diene monomer to prepare an
ethylene-aliphatic diene copolymer, and (b) modifying the
ethylene-aliphatic diene copolymer.
5. The method of preparing the poly(ethylene-aliphatic diene)
copolymer according to claim 4, wherein the step (a) is carried out
by living polymerization in the presence of a metallocene
catalyst.
6. The method of preparing the poly(ethylene-aliphatic diene)
copolymer according to claim 5, wherein a central metal of the
metallocene catalyst is a group 4 transition metal, a ligand of the
metallocene catalyst is cyclopentadienyl or derivatives thereof;
fluorenyl or derivatives thereof; indenyl or derivatives thereof,
and a structure of the metallocene catalyst is bridged or
non-bridged structure.
Description
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a poly(ethylene-aliphatic diene)
copolymer having improved properties such as adhesion, printability
and the like by introducing a variety of functional groups, and a
preparation method thereof.
Description of the Related Art
Thermoplastic elastomers (TPEs) consist of soft segments having
elasticity and hard segments preventing deformation due to
thermoplasticity. TPEs may be formed by a method identical to a
method of processing thermoplastics. TPEs also have elasticity,
which is a property of thermoplastic rubber, at room temperature.
By varying amounts of soft segments and hard segments in TPEs, TPEs
having various properties may be produced.
TPEs are utilized as a material in various fields such as shoes,
adhesives, vehicles, industrial supplies, constructions, civil
engineering, marine industries, wires, cables, electronic devices,
electrical appliances, sports equipment, packing materials, medical
supplies and the like. TPEs are also used in large quantities as a
plastic conditioner or as compatibilizers for polymer alloys. The
alloys using TPEs are utilized in electrical and electronic
devices, cameras and the like. In addition, TPEs may provide
properties such as conductivity, photosensitivity, selective
separation and the like and, as such, may be utilized in fields
requiring high functionality such as electrical engineering,
optics, medicine, and printing. TPEs are attracting considerable
attention due to such high functionality thereof. Particularly, in
medical supplies, TPEs may be utilized as a high purity rubber
material, without a vulcanization agent. People have great interest
and are studying for such an advantage of TPEs.
Research and development for types of soft segments and hard
segments, molecular weights, and arrangements of TPE products are
being conducted. Thus, TPE products having high performance and
functionality are being produced and TPE product types are being
varied. In addition, demand for TPEs is increasing every year due
to continuous use development and concern on the environment. As a
result, TPE market is being expanded actively.
TPEs are classified into thermoplastic olefinic elastomers (TPO),
thermoplastic styrenic block copolymers (SBC), thermoplastic
polyurethanes (TPU), thermoplastic polyamides (TPAE), thermoplastic
polyester elastomers (TPEE), and the like.
Most TPO based TPEs are block copolymers in which polypropylene,
polystyrene, polyethylene, nylon, styrene-acrylonitrile and the
like, which are hard, and ethylene propylene diene (EPDM) rubber,
natural rubber, styrene-butadiene rubber (SBR) and the like, which
are soft, are copolymerized. Among these, a random block copolymer
consisting of ethylene/.alpha.-olefin is the most widely utilized.
Most TPO based TPEs are a random copolymer. Recently, to improve
properties of TPO based TPEs, methods using metallocene catalysts
or introducing living polymerization has been proposed
(Olefin-diene Copolymer, Korean Application Pub. Nos. 2012-0052385
and 2011-0114475).
As SBC based TPEs, Kraton Performance Polymers Inc. prepares and
sells SBS (polystyrene/polybutylene binary copolymer), SEPS
(polystyrene/poly(ethylene-propylene)/polystyrene terpolymer), SEBS
(polystyrene/poly(ethylene-butylene))/polystyrene terpolymer) and
the like under the registered trademark "Kraton". As similar
products to the SBC based TPEs, a variety of polymers such as
Solprene and Calprene series of Dynasol, SEPTON of KURARAY CO.,
LTD., and the like are commercially available.
Molecules of TPO based or SBC based TPEs are non-polar. Thus, the
TPO based or SBC based TPEs do not adhere easily to metal, wood and
plastic materials, and do not have miscibility with other polymers.
For these reasons, use of the TPO based or SBC based TPEs is
limited.
PRIOR ART LITERATURE
Patent Literature
(PATENT LITERATURE 1) Korean Application Pub. No. 2012-0120430
SUMMARY OF THE INVENTION
Therefore, the present invention has been made in view of the above
problems, and it is an object of the present invention to provide a
copolymer modified with functional groups having high reactivity
for the aliphatic dienes using aliphatic diene as monomers of TPO
based TPEs, and having improved miscibility, adhesivity,
printability and scratch resistance, as a result of studies into
TPE modification for improvement in miscibility with and adhesivity
to other polymers.
It is another object of the present invention to provide a
poly(ethylene-aliphatic diene) copolymer having improved properties
such that the copolymer may be utilized in a variety of fields, and
a method preparing the same.
In accordance with the present invention, the above and other
objects can be accomplished by the provision of a
poly(ethylene-aliphatic diene) copolymer comprising an ethylene
block and aliphatic diene block, wherein a portion of the aliphatic
diene block is modified through substitution with a functional
group selected from the group consisting of sulfides, hydroxyls,
epoxies, amines, carboxylic acids, silane groups and combinations
thereof.
Concretely, the aliphatic diene block modified with the functional
group may be represented by Formula 1 below:
##STR00001##
Wherein, R.sub.1 is a linear or branched C1-C20 alkyl group, and
R.sub.2 is selected from OH, C(.dbd.O)OH, S(R.sub.3),
NR.sub.4R.sub.5 and SiR.sub.6R.sub.7R.sub.8, wherein R.sub.1 and
R.sub.2 bind together to form an epoxy ring, R.sub.3 is H or a
C1-C30 alkyl group, R.sub.4 and R.sub.5 are the same or different,
and are hydrogen, an C1-C10 alkyl group, a C3-C10 cycloalkyl group
or an aryl group of C4-C15, and R.sub.6 to R.sub.8 are the same or
different, and are hydrogen, an C1-C10 alkyl group, a C3-C10
cycloalkyl group or a C6-C15 aryl group, with the proviso that at
least one of R.sub.6 to R.sub.8 is a C1-C10 alkoxy group or a
functional group substituted with the alkoxy group of C1-C10 and
all of R.sub.6 to R.sub.8 are not H.
In accordance with another aspect of the present invention, there
is provided a method of preparing a poly(ethylene-aliphatic diene)
copolymer comprising:
(a) polymerizing ethylene with a conjugated diene monomer to
prepare an ethylene-aliphatic diene copolymer, and
(b) modifying the ethylene-aliphatic diene copolymer.
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The present invention proposes a copolymer having greatly improved
properties by modifying a vinyl functional group of aliphatic diene
in a copolymer consisting of an ethylene block and aliphatic diene
block.
Preferably, the copolymer is a block copolymer wherein ethylene
represented by a --[CH.sub.2--CH.sub.2].sub.l-- block and an
aliphatic diene monomer represented by
--[CH.sub.2--CH(--R.sub.1--R.sub.2)].sub.m-- are copolymerized.
Here, the aliphatic diene block is substituted with a block
represented by Formula 1 below and thereby, the copolymer is
modified:
##STR00002##
wherein, R.sub.1 is a C1-C20 linear or branched alkyl group,
R.sub.2 is selected from OH, C(.dbd.O)OH, S(R.sub.3),
NR.sub.4R.sub.5 and SiR.sub.6R.sub.7R.sub.8, wherein R.sub.1 and
R.sub.2 bind together to form an epoxy ring, R.sub.3 is hydrogen or
a C1-C30 alkyl group, R.sub.4 and R.sub.5 are the same or different
and are hydrogen, a C1-C10 alkyl group, a C3-C10 cycloalkyl group
or a C4-C15 aryl group, and
R.sub.6 to R.sub.8 are the same or different and are hydrogen, a
C1-C10 alkyl group, a C3-C10 cycloalkyl group or a C6-C15 aryl
group, with the proviso that at least one of R.sub.6 to R.sub.8 is
a C1-C10 alkoxy group or a functional group substituted with the
C1-C10 alkoxy group and all of R.sub.6 to R.sub.8 are not
hydrogen.
R.sub.1 of the aliphatic diene block is a C2-C20 linear or branched
alkyl group. For example, R.sub.1 may be substituted with an alkyl
group such as ethyl, propyl, isopropyl, butyl, pentyl, hexyl,
heptyl, octyl, nonyl and the like, and the C2-C20 linear or
branched alkyl group may be substituted with at least one of alkyl
groups such as a methyl, ethyl, propyl, isopropyl, butyl, pentyl,
hexyl, heptyl, octyl and nonyl group.
The aliphatic diene monomer may be a C4-C20 conjugated diene based
monomer such as 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,2-dimethyl-1,3-butadiene,
1,4-dimethyl-1,3-butadiene, 1-ethyl-1,3-butadiene,
3-butyl-1,3-octadiene, 1,3-hexadiene, 4-methyl-1,3-pentadiene,
1,3-pentadiene, 3-methyl-1,3-pentadiene,
2,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene and the like.
As an embodiment of the present invention, 1,3-butadiene is
utilized.
The aliphatic diene monomer has two double bonds. One double bond
is polymerized with ethylene to form a main chain and the other
double bond is used to introduce a variety of functional groups
according to a modification method described below.
The functional groups which may be introduced may be S(R.sub.3),
OH, epoxy, 1, C(.dbd.O)OH or Si(OR.sub.4).sub.3, wherein R.sub.3
and R.sub.4 are the same or different and may be a C1-C8 linear or
branched alkyl group. By introducing the functional groups,
properties of the copolymer may be improved. Particularly, since
the functional group has high reactivity, adhesion of the polymer
to other materials such as substrates by introducing a functional
group is improved. In addition, a double bond in an aliphatic diene
is polymerized with a functional group and, as such, mechanical
properties of the polymer are improved.
By introducing the functional group, properties of thermoplastic
elastomer (TPE) are improved within a certain substitution degree,
preferably within the range of 5 to 50%, more preferably within the
range of 10 to 30%. Here, when substitution degree is high,
adhesion and printability are improved, however, mechanical
properties may be reduced. Thus, substitution degree should be
properly controlled within the above ranges.
Furthermore, the average molecular weight of a
poly(ethylene-aliphatic diene) copolymer of Formula 1 may be
controlled within the range of 10,000 to 1,000,000, the average
molecular weight of a poly(styrene) block copolymer may be
controlled within the range of 10,000 to 50,000. Here, the range of
the molecular weight distribution degree of the
poly(ethylene-aliphatic diene) copolymer is preferably 1.2 to 3.0.
In addition, the average molecular weight of the
poly(ethylene-aliphatic diene) copolymer is within the range of
20,000 to 3,000,000.
The poly(ethylene-aliphatic diene) copolymer of Formula 1 of the
present invention is prepared in accordance with steps described
below:
a) polymerizing ethylene with a conjugated diene monomer to prepare
an ethylene-aliphatic diene copolymer, and
b) modifying the ethylene-aliphatic diene copolymer to prepare a
poly(ethylene-aliphatic diene) copolymer.
Hereinafter, each step will be described in more detail.
First, in step a), ethylene is polymerized with the conjugated
diene monomer to prepare an ethylene-aliphatic diene copolymer.
The polymerization reaction may be carried out using any one of
mass polymerization, solution polymerization, emulsion
polymerization, suspension polymerization, slurry polymerization,
vapor phase polymerization, and the like. Mechanism polymerization
methods such as step polymerization, chain polymerization, ion
polymerization, radical polymerization and living polymerization
are applicable to the present invention. Preferably, living
polymerization using metallocene catalysts is utilized in the
present invention.
The metallocene catalysts have even active sites. Thus, by using
metallocene catalysts, a narrow molecular weight distribution of
the copolymer is obtained and it is easy to copolymerize ethylene
with a conjugated diene monomer. In addition, the conjugated diene
monomer is copolymerized evenly with ethylene and, as such, an even
molecular weight distribution of the copolymerized conjugated diene
is obtained.
Here, the metallocene catalysts are not limited to specific types.
Any catalysts utilized in TPO polymerization are applicable. As an
exemplary embodiment, central metals of the metallocene catalysts
are group 4 transition metals. Ligands of the metallocene catalysts
are cyclopentadienyl or derivatives thereof, fluorenyl or
derivatives thereof, or indenyl or derivatives thereof. Structures
of the metallocene catalysts are bridge or non-bridge structures.
The central metals of the metallocene catalysts are, preferably, Ti
or Zr. The ligands of the metallocene catalysts are, preferably,
indenyl or derivatives thereof. The structures of the metallocene
catalysts are, preferably, bridge structures. When the above
preferable examples are used in the polymerization reaction,
catalytic activity is superior.
An amount of the metallocene catalysts may be determined within a
range sufficient to induce a sufficient polymerization reaction.
The amount of the metallocene catalysts is not limited to specific
levels in the present invention. For example, the metallocene
catalysts may be utilized in an amount of 10-8 to 1 mol, preferably
10-7 to 10-1 mol, per unit volume (L) of a monomer, based on a
concentration of the central metals (M) of the transition metal
compounds.
The polymerization reaction may be batch, semi-continuous or
continuous reaction. When living polymerization is empolyed, any of
these types is possible.
In living polymerization, chain transfer reaction or termination
reaction does not occur. Although polymerization reaction is
terminated, polymerization activity is maintained in end portions
(both end portions or one end portion) of the polymer. Thus,
subsequent graft polymerization using an SBC based monomer may be
carried out continuously.
Here, temperature and pressure of reactors, in which polymerization
reaction is carried out, may be determined considering
polymerization reaction efficiency, dependent on types of reactions
and reactors. Thus, temperature and pressure of reactors are not
limited to specific values. For example, the polymerization
reaction may be carried out at a temperature of -50 to 500.degree.
C., preferably 0 to 150.degree. C. and at a pressure of 1 to 3000
atm, preferably 1 to 500 atm.
Here, by using the metallocene catalysts described previously to
prepare the poly(ethylene-aliphatic diene) copolymer, a
microstructure of the copolymer may be easily changed. Thus, the
poly(ethylene-aliphatic diene) copolymer having a large amount of
conjugated diene monomer may be prepared. In addition, the
poly(ethylene-aliphatic diene) copolymer having a large molecular
weight and desired properties may be prepared.
Namely, the ratio of the ethylene polymerized with the
poly(ethylene-aliphatic diene) copolymer to the conjugated diene
monomer may be in the range of 1:0.1 to 1:10, preferably in the
range of 1:0.1 to 1:5, more preferably in the range of 1:0.1 to
1:1. The average molecular weight (Mw) of the resultant
poly(ethylene-aliphatic diene) copolymer may be in the range of
10,000 to 1,000,000, preferably in the range of 50,000 to
800,000.
Solvents, initiators, polymerization regulators utilized in the
polymerization reaction of the present invention are not
specifically limited.
The solvents may be hydrocarbons which do not react with living
anionic chain ends of a copolymer, are easily utilized in
commercial polymerization apparatus, and provide proper solubility
to polymers. For example, non-polar aliphatic hydrocarbons, in
which ionization hydrogen is generally deficient, are suitable. As
generally utilized solvents, there are cyclic alkanes, for example,
cyclopentane, cyclohexane, cycloheptane and cyclooctane. All of the
above cyclic alkanes are relatively non-polar. Other solvents may
be selected from solvents which are already known to a person
skilled in the art and effectively react under predetermined
conditions, particularly, temperature.
The polymerization initiators comprise, for example, alkyl lithium
compounds such as s-butyl lithium, n-butyl lithium, t-butyl lithium
and amyl lithium, and other organolithium compounds such as
analogous compounds thereof. In addition, the polymerization
initiators comprise di-initiators such as a di-sec-butyl lithium
adduct of m-diisopropyl benzene. Here, an amount of the
polymerization initiator may be calculated based on one initiator
molecular per a desired polymer chain, in a polymerization mixture
(comprising monomers and solvents).
The polymerization regulators may control a microstructure of the
poly(ethylene-aliphatic diene) copolymer by regulating contents of
the ethylene block and conjugated diene block. In addition, the
polymerization regulators may control the grafting degree of a
graft-polymerized poly(styrene) block copolymer after controlling
an amount of the conjugated diene.
Next, by modification reaction of the ethylene-aliphatic diene, the
poly(ethylene-aliphatic diene) copolymer of Formula 1 is prepared.
The modification reaction is varied according to introduced
functional groups. Hereinafter, a modification reaction for each
functional group will be described. Here, as aliphatic diene,
1,4-butadiene is utilized for convenience.
(1) OH Modification Method
To introduce a hydroxyl group to the polybutadiene block, the
poly(ethylene-butadiene) is reacted with a borane compound and then
is treated with an oxidizing agent, as described in Reaction
Formula 1 below:
##STR00003##
In the above reaction, hydroboration reaction occurs. Namely, the
poly(ethylene-butadiene) is converted into alkyl borane using a
borane compound, HBR.sub.4. Here, the alkyl borane is changed to a
hydroxyl group using an oxidizing agent. Namely, oxidation reaction
occurs.
Such reactions are carried out according to methods described in
literature below: [J. M. Clay, E. Vedejs, Hydroboration with
Pyridine Borane at Room Temperature, J. Am. Chem. Soc., 2005, 127,
5766-5767], [G. W. Kabalka, T. M. Shoup, N. M. Goudgaon, Sodium
perborate: Mild and Convenient Reagent for Efficiently Oxidizing
Organoboranes, J. Org. Chem., 1989, 5930-5933], [P. K. Patra, K.
Nishide, K. Fuji, M. Node, Dod-S-Me and Methyl 6-Morpholinohexyl
Sulfide (MMS) as New Odorless Borane Carriers, Synthesis, 2004,
1003-1006], and [P. V. Ramachandran, M. P. Jennings, An Exceptional
Hydroboration of Substituted Fluoroolefins Providing Tertiary
Alcohols, Org. Lett., 2001, 3, 3789-3790].
Available borane compounds comprise BH.sub.3, B.sub.2H.sub.6,
9-BBN(9-Borabicyclo(3.3.1)nonane), catecholborane, thexylborane
(ThxBH.sub.2), thexylchloroborane (ThxBHCl), disiamylborane
(Sia.sub.2BH), dicyclohexylborane (Chx.sub.2BH) and the like.
As the oxidizing agent, H.sub.2O.sub.2, NaOH, H2O and the like may
be utilized.
Preferably, in Reaction Formula 1, BH.sub.3/H.sub.2O.sub.2 or
9-BBN/NaOH may be utilized. Here, reaction conditions, which are
not specifically limited, may be conditions described in the above
literature.
(2) C(.dbd.O)OH Modification Method
To introduce a carboxylic acid group to the polybutadiene block,
the poly(ethylene-butadiene) is treated with carbon dioxide as
described in Reaction Formula 2 below:
##STR00004##
If considered necessary for the above reaction, a catalyst may be
utilized. For example, Williams et al. substituted styrenes with
carboxylic acid using CO.sub.2 in the presence of a nickel
catalyst/diethylzinc reductant [C. M. Williams, J. B. Johnson, T.
Rovis, A nickel-catalyzed reductive carboxylation of styrenes using
CO2 proceeds under mild conditions using diethylzinc as the
reductant. The catalyst system is very robust and will fixate CO2
in good yield even if exposed to only an equimolar amount
introduced into the headspace above the reaction. J. Am. Chem.
Soc., 2008, 130, 14936-14937]. M. D. Greenhalgh et al. reacted aryl
alkenes with CO.sub.2 and EtMgBr as a hydride in the presence of a
FeCl.sub.2 catalyst, bis(imino)pyridine, to generate .alpha.-aryl
carboxylic acids [M. D. Greenhalgh, S. P. Thomas,
Hydrocarboxylation of aryl alkenes in the presence of FeCl.sub.2 as
precatalyst, bis(imino)pyridine as ligand, an atmospheric pressure
of CO.sub.2, and EtMgBr as a hydride source gives .alpha.-aryl
carboxylic acids in excellent yields and with near-perfect
regioselectivity. Various, electronically differentiated aryl
alkenes were transformed to the corresponding .alpha.-aryl carbo
xylic acids in very good isolated yield. J. Am. Chem. Soc., 2012,
134, 11900-11903]. Reaction conditions of Reaction Formula 2 may be
determined by referring to the above literature.
(3) S(R.sub.3) Modification Method
To introduce a sulfide group to the polybutadiene block, the
poly(ethylene-butadiene) is reacted with a thiol compound as
described in Reaction Formula 3 below:
##STR00005##
In the above formula, R.sub.3 is hydrogen and a C1-C30 alkyl
group.
The above reaction may be carried out using methods described in
literature as follows: a thiol-ene reaction method using CeCl.sub.3
[C. C. Silveira, S. R. Mendes, F. M. Libero, The anti-Markovnikov
addition of thiols to alkenes using CeCl.sub.3 as catalyst leads to
products in very good yields. The reaction occurred under
solvent-free conditions at room temperature, Synlett, 2010,
790-792], a method of adding water [B. C. Ranu, T. Mandal, A highly
selective anti-Markovnikov addition of thiols to unactivated
alkenes in water at room temperature without any additive is a very
simple and efficient method for the synthesis of linear thioethers.
Synlett, 2007, 925-928], and the like.
Here, the thiol compound (HSR.sub.3) is not specifically limited,
however, an aliphatic thiol compound is preferably utilized. As a
representative example, C1-C30 alkane thiols are possible. The
C1-C30 alkane thiols comprise, for example, 1-pentanethiol,
1-hexanethiol, 1-heptanethiol, 1-octanethiol, 1-decanethiol,
1-dodecane-thiol and the like.
Here, conditions of the reaction, which are not specifically
limited, may be thiol-ene reaction conditions publicly known or
methods described in the above literature.
(4) Epoxy Cyclization Method
Epoxy cyclization means that some alkyl groups of aliphatic diene
bind together to form epoxy rings. The epoxy cyclization may be
carried out by a variety of epoxidations such as Jacobsen-Katsuki
Epoxidation, Prilezhaev Reaction, Sharpless Epoxidation, Shi
Epoxidation and the like.
Concretely, the epoxy cyclization may be carried out by treating
the poly(ethylene-butadiene) with an oxidizing agent as illustrated
in Reaction Formula 4 below and if considered necessary, a catalyst
may be utilized.
##STR00006##
For an example, in Jacobsen-Katsuki Epoxidation, a Mn-salen
catalyst and an oxidizing agent may be utilized. The epoxidation
may be carried out referring to literature as follows: E. N. J
acobsen, W. Zhang, A. R. Muci, J. R. Ecker, L. Deng, Highly
Enantioselective Epoxidation Catalysts Derived from
1,2-diaminocyclohexane, J. Am. Chem. Soc., 1991, 113, 7063-7064,
and [B. D. Brandes, E. N. Jacobsen, Highly Enantioselective
Epoxidation Catalysts Derived from 1,2-diaminocyclo hexane, J. Org.
Chem., 1994, 59, 4378-4380].
The Prilezhaev Reaction utilizes 3-chloroperoxybenzoic acid
(MCPBA). The reaction may be carried out referring to literature as
follows: [N. K. Jan a, J. G. Verkade, Use of a solvent with greater
density than the fluorous phase is an alternative to the U-tube
method in phase-vanishing reactions in cases where both reactants
are less dense than the fluorous phase, Org. Lett., 2003, 5,
3787-3790] and [Y.-B. Kang, L. H. Gade, A clean and efficient and
metal-free diacetoxylation reaction of alkenes using commercially
available peroxyacids as oxidants is catalyzed by triflic acid.
This method enables also oxidative lactonizations of unsaturated
carboxylic acids in good to high yields. J. Org. Chem., 2012, 77,
1610-161 5].
The Sharpless Epoxidation utilizes t-butyl hydroperoxide as an
oxidizing agent and Ti(OiPr).sub.4 as a catalyst. The epoxidation
may be carried out referring to literature as follows: [Johnson, R.
A. and Sharpless, K. B. Comp. Org. Syn. 1991, 7, 389.about.436],
[Huft, E. Top. Curr. Chem. 1993, 164, 63.about.77], [Katsuki, T.
and Martin, V. S. Org. React. 1996, 48, 1.about.300], and
[Pfenninger, A. Synthesis, 1986, 89.about.116].
The Shi epoxidation means that a compound reacts with KHSO.sub.5
after reacting with an oxidizing agent, 2
KHSO.sub.5.KHSO.sub.4.K.sub.2SO.sub.4. The epoxidation may be
carried out referring to literature as follows: [Z.-X. Wang, Y. Tu,
M. Frohn, J.-R. Zhang, Y. Shi, An Efficient Catalytic Asymmetric
Epoxidation Method, J. Am. Chem. Soc., 1997, 119, 11224-11235], [H.
Tian, X. She, L. Shu, H. Yu, Y. Shi, Highly Enantioselective
Epoxidation of cis-Olefins by Chiral Dioxirane, J. Am. Chem. Soc.,
2000, 122, 11551-11552], [N. Nieto, I. J. Munslow, H.
Fernandez-Perez, A. Vidal-Ferran, Exploring Substrate Scope of
Shi-Type Epoxidations, Synlett, 2008, 28 56-2858], and [B. Wang, O.
A. Wong, M.-X. Zhao, Y. Shi, Asymmetric Epoxidation of
1,1-Disubstituted Terminal Olefins by Chiral Dioxirane via a
Planar-like Transition State, J. Org. Chem., 2008, 73,
9539-9543].
(5) Amine Modification Method
To introduce an amine group to the polybutadiene block, the
poly(ethylene-butadiene) is reacted with an amine compound by
hydroamination reaction, as described in Reaction Formula 5
below:
##STR00007##
In the above formula, R.sub.4 and R.sub.5 are the same or
different, and hydrogen, a C1-C10 alkyl group or a C3-C10
cycloalkyl group, and a C6-C15 aryl group).
The amine compounds (H--NR.sub.4R.sub.5), which are not
specifically limited, may be, for example, ammonia, methylamine,
ethylamine, dimethylamine, methylethylamine and the like.
The above reaction, if considered as necessary, may utilize a
catalyst. Here, the catalyst may be a transition metal
catalyst.
Such a reaction may be carried out referring to literature as
follows: [Jain, A. Hydroamination-Direct Addition of Amines to
Alkenes and Alkynes, Kai C. Hultzsch. "Catalytic Asymmetric
Hydroamination of Non-activated Olefins", Organic &
Biomolecular Chemistry, 2005 3 (10): 1819.about.1824], [Hartwig, J.
F., Development of Catalysts for the Hydroamination of Olefins,
Pure Appl. Chem. 2004, 76 (3): 507.about.516], [Shi, Y. H et al,
Titanium Dipyrrolylmethane Derivatives: Rapid Intermolecular Alkyne
Hydroamination", Chemical Communications 2003, 5 (5):
586.about.587], [Pohlki, F., Doye, S. (2003), "The Catalytic
Hydroamination of Alkynes". Chemical Society Reviews, 32 (2):
104.about.114] and [Ryu J S et al., Organolathanide-catalyzed
Regioselective Intermolecular Hydroamination of Alkenes, Alkynes,
Vinylarenes, Di- and Trivinylarenes, and Methylenecyclopropanes,
Scope and Mechanistic Comparison to Intramolecular
Cyclohydroaminations. J Am Chem. Soc. 2003 Oct. 15;
125(41):12584-605].
(6) SiR.sub.6R.sub.7R.sub.8 Modification Method
To introduce a silane group to the polybutadiene block, the
poly(ethylene-butadiene) is reacted with a silane compound as
illustrated in Reaction Formula 6 below:
##STR00008##
In the above formula, R.sub.6 to R.sub.8 are the same or different
and may be hydrogen, OH, a C1-C10 alkyl group, a C3-C10 cycloalkyl
group, a C1-C10 alkoxy group or a C6-C15, with the proviso that all
of R.sub.6 to R.sub.8 are not hydrogen, and X is a leaving group
and H or a halogen group.
A silane compound (HSiR.sub.6, R.sub.7R.sub.8) utilized in the
above reaction is an alkoxysilane compound. The silane compound
(HSiR.sub.6, R.sub.7R.sub.8), which is not specifically limited,
may be, preferably, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltriethoxysilane,
methyltrimethoxysilane, methyltriethoxysilane,
methyltripropoxysilane, propylethyltrimethoxysilane,
ethyltriethoxysilane and the like.
To introduce ethoxysilane to the poly(ethylene-butadiene),
SiH(CH.sub.3)(OEt).sub.2 as a silane compound and PtO.sub.2 as a
catalyst may be utilized according to a method proposed by N.
Sabourault et al (N. Sabourault, G. Mignani, A. Wagner, C.
Mioskowski, Platinum oxide is a versatile and powerful
hydrosilylation catalyst for alkenes. Tolerance of various
functional groups (amines, epoxides, nitriles, carbon acids and
esters), highly reproducible results and easy removal make this
catalyst a useful tool for hydrosilylation. Org. Lett., 2002, 4,
2117-2119). Reaction conditions of Reaction Formula 6 may be
determined referring to the above literature.
Some aliphatic diene repeat units of the poly(ethylene-aliphatic
diene) copolymer modified by the above reaction are substituted
with a sulfide, hydroxy, epoxy, amine, carboxyl or silane group.
Since the groups have high reactivity, the groups provide superior
miscibility, adhesivity, printability and scratch resistance to
other materials (for example, substrate). In addition, the
functional groups bind with a portion of double bonds of the
aliphatic diene and, as such, mechanical properties are
improved.
As a result, the poly(ethylene-aliphatic diene) copolymer of the
present invention may be utilized instead of the prior
thermoplastic elastomers (TPEs). Particularly, the
poly(ethylene-aliphatic diene) copolymer of the present invention
may be utilized in fields requiring superior adhesivity and
printability such as, for example, shoes, adhesives, vehicles,
industrial supplies, constructions, civil engineering, marine
industries, wires, cables, electronic devices, electrical
appliances, sports equipment, packing materials, medical supplies,
printers, compatibilizers and the like.
In the following examples, the present invention will be described
in more detail. It should be understand that the examples are
merely to concretely explain the spirit of the invention and
therefore, there is no intent to limit the invention to the
examples.
Preparation Example 1
Poly(ethylene-butadiene) Copolymer Synthesis
400 mL of toluene, 13.58 g (0.25 mol) of 1,3-butadiene and ethylene
were added to two 500 mL reactors at 0.4 MPa for 30 minutes.
To prepare a catalyst solution, 2.5 mol of
1,2,4-trimethylcyclopentadienyl 2,6-isopropylaryloxo titanium
dichloride as a catalyst and methylaluminoxane as a cocatalyst, in
a 1:3000 molar ratio between the 1,2,4-trimethylcyclopentadienyl
2,6-isopropylaryloxo titanium dichloride and the methylaluminoxane,
were dissolved in toluene.
Temperatures of the reactors were maintained at 50.degree. C. After
adding the catalyst solution to the reactors, polymerization was
carried out for 30 minutes. Thereafter, methanol and hydrochloric
acid were added to the reactors to terminate polymerization. Next,
reaction products were isolated and then dried at reduced pressure
at 60.degree. C. for 6 hours, to obtain the
poly(ethylene-butadiene) copolymer. The prepared
poly(ethylene-butadiene) copolymer was directly utilized in a next
stage without additional purification.
Example 1
Preparation of poly(ethylene-butadiene) Copolymer Modified with
OH
Using the poly(ethylene-butadiene) copolymer in Preparation Example
1, a poly(ethylene-butadiene) copolymer modified with OH was
prepared.
The poly(ethylene-butadiene) copolymer of Preparation Example 1 was
dissolved in toluene. Thereafter, 9-BBN (1.0 eq) was added to the
reactor and then a reaction was carried out for 1 hour. Thereafter,
after adding a large amount of NaOH/H.sub.2O.sub.2 to the reactor,
reaction was carried for 3 hours. Finally, methanol and
hydrochloric acid were added to the reactor to terminate the
polymerization reaction.
Example 2
Preparation of poly(ethylene-butadiene) Copolymer Modified with
Carboxylic Acid
Using the poly(ethylene-butadiene) copolymer prepared in
Preparation Example 1, a poly(ethylene-butadiene) copolymer
modified with carboxylic acid was prepared.
The poly(ethylene-butadiene) copolymer Of Preparation Example 1 was
dissolved in toluene. Thereafter, a Ni(.sub.acac).sub.2 catalyst
(0.1 eq) was added to the reactor. Thereafter, reductants,
Et.sub.2Zn (2.5 eq) and Cs.sub.2CO.sub.3 (0.2 eq), which were
dissolved in THF, were added to the reactor. Thereafter, CO.sub.2
was added to the reactor. Polymerization was carried out at
23.degree. C. for 10 hours. Finally, methanol and hydrochloric acid
were added to terminate the polymerization reaction.
Example 3
Preparation of poly(ethylene-butadiene) Copolymer Modified with
Sulfide (--SCH.sub.3)
Using the poly(ethylene-butadiene) copolymer prepared in
Preparation Example 1, a poly(ethylene-butadiene) copolymer
modified with sulfide was prepared.
The poly(ethylene-butadiene) copolymer of Preparation Example 1 was
dissolved in toluene. Thereafter, CH.sub.3--SH (1.1 eq) and water
were added to the reactor and then reactor was maintained at
23.degree. C. for 3 hours such that polymerization proceeded.
Finally, methanol and hydrochloric acid were added to the reactor
to terminate the polymerization reaction.
Example 4
Preparation of poly(ethylene-butadiene) Copolymer Modified with
Epoxy Ring
Using the poly(ethylene-butadiene) copolymer prepared in
Preparation Example 1, a poly(ethylene-butadiene) copolymer
modified with epoxy was prepared.
The poly(ethylene-butadiene) copolymer of Preparation Example 1 was
dissolved in toluene. Thereafter, 9-BBN (1.0 eq) was added to the
reactor and then the solution was reacted for 1 hour. Thereafter, a
large amount of NaOH/H.sub.2O.sub.2 was added to the reactor.
Finally, methanol and hydrochloric acid were added to the solution
to terminate the polymerization reaction.
Example 5
Preparation of poly(ethylene-butadiene) Copolymer Modified with
Amine
Using the poly(ethylene-butadiene) copolymer prepared in
Preparation Example 1, a poly(ethylene-butadiene) copolymer
modified with amine was prepared.
The poly(ethylene-butadiene) copolymer of Preparation Example 1 was
dissolved in toluene. Thereafter, a Ni(.sub.acac).sub.2 catalyst
(0.1 eq), and reductants, Et.sub.2Zn (2.5 eq) and Cs.sub.2CO.sub.3
(0.2 eq), which were dissolved in THF, were added to the reactor.
Thereafter, CO.sub.2 was added to the reactor and then the reactor
was maintained at 23.degree. C. for 10 hours such than
polymerization proceeded. Finally, methanol and hydrochloric acid
were added to terminate the polymerization reaction.
Example 6
Preparation of poly(ethylene-butadiene) Copolymer Modified with
Methyldiethoxy Silane
Using the poly(ethylene-butadiene) copolymer prepared in
Preparation Example 1, a poly(ethylene-butadiene) copolymer with
silane was prepared.
The poly(ethylene-butadiene) copolymer of Preparation Example 1 was
dissolved in toluene. Thereafter, to the reactor,
Si(H)(CH.sub.3)(OEt).sub.2 was added and then a 0.01 mol %
PtO.sub.2 catalyst was added. The reactor was maintained at
85.degree. C. for hours such that polymerization proceeded.
Finally, methanol and hydrochloric acid were added to the reactor
to terminate the polymerization reaction.
Comparative Example 1
Poly(ethylene-butadiene-styrene) Terpolymer
To prepare a catalyst solution, 2.5 mol
1,2,4-trimethylcyclopentadienyl 2,6-isopropylaryloxo titanium
dichloride as a catalyst, and methylaluminoxane as a cocatalyst in
a 1:3000 molar ration between the 1,2,4-trimethylcyclopentadienyl
2,6-isopropylaryloxo titanium dichloride and the methylaluminoxane
were dissolved in toluene.
Reactor temperatures was maintained at 50.degree. C. After adding
the above catalyst solution to the reactor, polymerization reaction
was carried out for 30 minutes. Thereafter, methanol and
hydrochloric acid were added to the reactor such that the
polymerization reaction was terminated. Next, reaction product was
isolated and then dried at reduced pressure at 60.degree. C. for 6
hours, to obtain the poly(ethylene-butadiene) copolymer.
Experimental Example 1
Spectroscopic Analysis of Copolymers
Properties of the copolymers prepared in Examples 1 to 3 were
analyzed using GPC and DSC instruments. The results are summarized
in Table 1.
(1) Gel permeation chromatography (GPC): Average molecular weights
(Mw) and molecular weight distributions (Mw/Mn) of the
poly(ethylene-butadiene) copolymers were measured using a PL-GPC
210 system (Polymer Laboratories Ltd.). The measurements were
carried out at 140.degree. C.
(2) Differential scanning calorimetery (DSC): A glass transition
temperature (Tg) was measured using a PL-GPC 210 system (Polymer
Laboratories Ltd.).
(3) Substitution degree: The substitution degree for each
functional group was measured using a publicly method known.
TABLE-US-00001 TABLE 1 Molecular Average weight molecular
distributions Substitution Modified functional groups weight (Mw)
(Mw/Mn) Tg degree Example --OH 310,000 2.4 -45.degree. C. 44% 1
g/mol Example --CO.sub.2H 315,000 2.5 -42.degree. C. 41% 2 g/mol
Example --SCH.sub.3 285,000 2.4 -42.degree. C. 35% 3 g/mol Example
Epoxy 290,000 2.6 -39.degree. C. 40% 4 g/mol Example --NH.sub.2
295,000 2.7 -40.degree. C. 49% 5 g/mol Example --Si (CH.sub.3)
(OCH.sub.2CH.sub.5).sub.2 305,000 2.5 -41.degree. C. 35% 6
g/mol
Referring to above Table 1, the copolymers prepared in the present
invention have very narrow molecular weight distributions and glass
transition temperatures of -30.degree. C. to -50.degree. C.
Experimental Example 2
Property Analyses
To compare properties of the copolymers in the above examples and
comparative examples, adhesivities and heat resistances of the
copolymers were measured. Here, as a control 1, a
poly(ethylene-butadiene) binary copolymer was utilized. Results are
summarized in Table 2 below.
For experiments, compounds prepared in examples and comparative
examples were dissolved in dimethylchloride. Thereafter,
approximately 3 g/m.sup.2 of a dried film was tamping on a
polyethylene terephthalate (PET) film and paper using an auto
proofer equipped with a gravure copper plate. Thereafter, a thick
film was formed by evaporative drying.
(1) To estimate adhesivities, cellophane tapes were attached on a
surface of the thick films having the compounds of the examples and
comparative examples and then the attached cellophane tapes were
detached instantaneously from the surfaces of the thick films. The
conditions of thick film surfaces were observed with the naked eye.
When the thick film was not detached, a score was 5. Whereas, when
most of the thick film was detached, a score was 1.
(2) To estimate printabilities, the thick films were observed with
the naked eye. When the printed condition was excellent, a score of
5 was given. Whereas, when the printed condition was the poorest, a
score of 1 was given.
(3) To estimate scratch resistances, surfaces of a thick films were
rubbed 20 times using an abrasion tester. The thick film surfaces
were observed with the naked eye. When the thick film surface was
not scratched, a score of 5 was given. Whereas, when entire surface
of the thick film was scratched, a score of 1 was given.
TABLE-US-00002 TABLE 2 Scratch Adhesivities Printabilities
resistances Example 1 5 5 5 Example 2 5 5 5 Example 3 5 5 5 Example
4 5 5 5 Example 5 5 5 5 Example 6 5 5 5 Comparative 2 2 3 Example
1
The above films comprising the poly(ethylene-aliphatic diene)
copolymer in accordance with the present invention showed superior
properties such as printability, adhesivity, scratch resistances,
and the like.
As is apparent from the above description, the present invention
provides a poly(ethylene-aliphatic diene) copolymer, a vinyl
functional group in aliphatic diene of which is modified with a
variety of functional groups, to improve functionality,
miscibility, adhesivity, printability and scratch resistance of the
copolymer such that the copolymer may be utilized in a variety of
fields.
Although the preferred embodiments of the present invention have
been disclosed for illustrative purposes, those skilled in the art
will appreciate that various modifications, additions and
substitutions are possible, without departing from the scope and
spirit of the invention as disclosed in the accompanying
claims.
* * * * *